Process of producing low boiling hydrocarbons



Ni. LEVINE March 4, 1941.

PROCESS 0F PRODUCINGV LOW BOILING HYDROCARBONS Original Filed April 8, 1937 Maf/als eyze,

, Patented Mar. 4, 1941 -PATENT OFFICE PROCESS OF PRODUCING LOW BOILING HYDROCARBONS Morris Levine, Pampa, Tex., assigner to Danciger Oil & Relineries, Inc., Tulsa, Okla.

Application April 8, 1937, Serial No. 135,811 Renewed April 16, 1940 8 Claims.

This invention relates to a method of producing low boiling point liquid hydrocarbons from norm mally gaseous hydrocarbons, more particularly to a method of producing gasoline-like products by polymerizing (or otherwise molecularly rearranging) normally gaseous hydrocarbons, such as gaseous olens, or gases containing them.

'I'he present method is based upon theeffect of certain catalysts in effecting thepolymerization of gaseous hydrocarbons and/or condensation of unsaturated hydrocarbons with aromatic or paramnic hydrocarbons to produce therefrom volatile, low boiling point hydrocarbon oils; As will be more particularly seen, the catalytic materials employed are cheap and readily available,

and the process itself is very flexible, being amenable for employment with different types of starting materials for the production of improved end products.

An object of the present invention is to provide a novel process of producing low boiling point hydrocarbons by the catalytically influenced polymerization of lighter hydrocarbons.

Another object is to provide an improved catalyst available for the polymerization and/or condensation of gaseous hydrocarbons, such as olens.

A further object is to produce improved types of volatile liquid hydrocarbons from cracked hydrocarbon gases.

Yet another object is to provide an improved apparatus for the production of volatile liquid hydrocarbons.

With these and other equally important objects in view, the invention comprehends the concept of subjecting light hydrocarbon fractions, such as olenic gas, at elevated temperature and at any predetermined pressure, to the action of a catalyst having the characteristics of nitrosyl chloride. In the preferred form of the process the operation is preferably carried out in the presence of a material having an accelerating or promoting effect on the reaction, such for example as bauxite, aluminum oxide and oxides of the alkaline earth metals, zinc oxide and stannic oxide.

The process is particularly adapted for the treatment of gaseous or volatile oleflns for the production of liquid gasoline-like hydrocarbons.

In order to more' readily explain the invention, a typical apparatus in which a preferred form of the process may be carried out is shown in the single figure of the accompanying drawing. It is to be understood, however, that the apparatus and process to be described is given merely to exemplify the underlyingl features of the invention and not as defining the only embodiment of the concept.

As noted above, improved volatile gasoline-like hydrocarbons may be produced by contacting olens, either in vapor or'liquid phase, and at elevated temperatures, in the presence of a catalyst having the characteristics of nitrosyl chloride. In the preferred method the materials to be polymerized and/or condensed are also contacted with a promoting agent, such as bauxite, zinc oxide, stannic oxide and other oxides, such as oxides of the alkaline earth metals, powdered aluminum, and the 1ike.

The process may be effectuated in a unit of the type shown in Fig.` 1. The unit includes a storage vessel I in which is stored the promoting agent, such as bauxite, preferably suspended in a carrying vehicle, such as a saturated or relatively saturated oil. This carrying medium may be, for example, gasoline, kerosene, or any other suitable hydrocarbon mixture. The material from storage vessel I may be passed through line 2, controlled by valve 2', to the mixing tank 3.

As shown the recycle stock, produced in a manner more fully to be explained, may be passed into the mixing tank through the line 4. The mixing tank 3 may be provided with any suitable type of agitating means so as to insure a satisfactory suspension of the solid promoting material in the liquid carrying vehicle.

The promoter stock prepared in mixing tank 3 is passed through line 5, controlled by valve 5', and is forced by the pump' 6 through the line 1 to the transfer line 8. Simultaneously the gases or gaseous mixture to be polymerized and/or condensed is taken from storage and passed through the line 9, controlled by valve 9', and forced by the pump I0 through the preheating unit I I. The preheating unit, as wil1 be understood, may be of any desired type and t vpacity and is merely conventionally illustrated on the drawing.

It is to be understood that the olefinic or other products to be treated accordingto the process may be forced through the heating cycle either in the gaseous or liquid phase, that it is to say it is to be understood that such gases, before passage to the heating unit, may be compressed to any desired degree.

The polymerizable material, preheated to the desired degree in preheater II, is forced through the transfer line 8 to the reactor I2., -The catalytic material, y preferably nitrosyl chloride, is fed from the tank I3 and valve I3' to the stream of preheated material in transit through the transfer line 8 t0 the reaction zone. Preferably,

' nary circumstances, such a reaction mixture pors. 'I'he liquid condensate from the gas sep'- .as show'n, the catalyst and the promoting material, s'uch as the bauxite. are added to a. rapid stream of preheated polymerizable material prior to admission to the reaction zone. The combinedv stream, that is to say, the mixture of the bauxite and its hydrocarbon vehicle, the polymerizable` gases, either in liquid or in vapor phase, and the nitrosyl chloride are thus thoroughly vintermixedl and are heated, in the reactor I2, to the desired reaction temperature. f

' It will be understood that the temperature to which the potentially reactive mass is heated vary, depending upon the type of starting material employed and the end products desired. For the f production-oL-for example, gasoline-like hydrocarbons from olenicvgases, the mixture may be heated inthe reaction zone I2 from atmospheric temperature up to 900 F., more or less. `In ordix preferably is heated to the order of `400 F. l

During the treatment in reaction zone I2 any y desired pressure may be imposd on the reaction mass. During this heat treatmentin the reactor, I2 polymerization and/or condensation-of the gaseous hydrocarbons is effected `through the'- catalytic agency of the nitrosyl chloride or its.. 1 equivalent in conjunction with the promoting material. The stream of reaction products, including the polymerized and/or condensed gases, are then passed' through the transfer linel I4, con troiled by the valve I4', to the vaportower I5. The valve, I 4 may be a pressure reduction valve and any desired pressure differential may be maintained between the vapor tower I5 and the.A reaction coil I2. In these circumstances, the more volatile components of thevreaction mixture may be vaporzed in the tower I5 by latent or sensible heat oi.' the mass. A p

The reflux liquid may suitably be introduced I through line I6, in order to control the temperature at the upper portlonof towe`r1I5, andcon'- sequently the characteristics of the veiiiuent `va-A arator 2I maybe utilized as the reuxing medium. In lieu of reuxing, it will be understood, that a knock-back coil maybe employed in the upper section of the' tower. Similarly, in the event it is found necessary or desirable lto .op-' erate thevrea'ction zone I2 at a relativelylow 1 temperature, areboiler I'I maybe employed to 1 obtain a satisfactory product inthe upper portion of the tower. -v j.

Overhead vapors of thedesired boiling point, in the preferred process vapors having' .the boil ing characteristics of, gasoline, "pass- 'overhead through theline I8 to the condenser I9. thev admixea ifuesirjed; withmethaneror cth hgh condenser I9, as will be understood,fthe`con. densible components" are liquefied, fr "The [con-. 1 densed product-is then passed vthrough lthielinelv 20 to the gasseparator 2|. The unc'r'nidensiblef,v gases are 'drawn oif"overhe ad through :theline 22 and valve 2 2-"and Vare passed toftheyaporre covery systeingorv are otherwise advantageouslydisposed of.' "'Fo`r instance,thegases,Y after/being deprivedofthegasoline constituents'whi'c they. Y' v still may have after"leavin`g"tlieggaslsepa at'or gas, may be vadded'to.'the gases leavng'gas sto'r age through lineff Iand y subjected againto a the line-likeconstituents, are,witmihra'wi-'th"rc u'gh the Y line 23 an'dvalve 23' and are passed to storage.A a v:

j by valve 3|', and subjected to any preferred type of treatment which is indicated by the charac- I lubricating oil, and the residue may then be sub-l jected to cracking.

levels. l'

'.is'utilized. as a carrier lforthe. bauxite may, as

admixture with nitrosyl chloride, through a tower jIn another phase of the present invention, ixnproved.- productsmayv be produced by subjecting Y lany.predeterxnir'led mixtures oiyolens or gases containing them, together with aromatic hydro-l 1-bpns, particularly' lthe lighter/fractions thereof,

" may be returned through the line 4, controlled by valve 4', to the' mixing tank to provide they suspension medium for the promoting material.

',The remainder of the condensate from the tower may be passed through ythe line 3l, controlled teristics of the stock. For example, the condensate may be passed through line 3I to a vapor or liquid phase cracking unit,gases from which arerretu'rned to the present system for further treatment. Again, if the characteristics of the condensate so indicate, such condensate may be v15V passed to a lubricating oil plant, that is to'say, the material may be subjected to any improved renery treatment for the separation of the It will be understood that, if desired, several liquid fractions of dierent characteristics may "-be withdrawn from the vapor tower I5 by the interposition'of trays and drawoffs at the desired 25 Itwill be appreciatedl that this type of process ,a

is very flexible and presents many possible modications. For example, the liquid medium which noted, be l'any desired oil fraction. It is to be understood, however, that the provision of a vliquid carrying vehicle for the bauxiteis not esf sentiaL. that is to say, the bauxite may be car-y -ried into the reaction system without employing a liquid vehicle.

' Again, it will be appreciated that the essential reactions involved may be effectuated by passing ya mixture vof the polymerizable or condensable gases, particularly in the liquid phase, andl in 40 packedwiththe bauxite. Yet again the gases undergoing treatment may be compressed to thev liquid phase and this liquid phase itself employed as thecarrying vehicle for the promoting lmaterial. 'Y

- In a further renement of the process the overhead'm'aterial from the vapor tower may be fractionated and'any given proportionof the-lighter Y reaction products may berecycled directly to, and beretreated'in, the system.-

carbons,. to the type of treatment Vmentioned.'l For-this purpose aromatic'or benzene hydrocarmay te combinedwith the stream o f 'unsaturated f hydrocarbons either'priof tov passage oi?` the lat-" ter tliroughfthe preheater I,I, i or such aromatic hydrocarbons 'may be admixedzwith the streaml i he line 8. In'thesevcircumstances'the, material. facilitates the condensation `of s 'c` hydrocarbons and the aromatic hyproduce improved types. of hydror v In modification ofthe invenl f lbel'mderstood, the aromatic;.hydro-'.v action.: which .is to be processed in the y, be l utilized asthe carrying vehicle C' auxitevQor equivalent promoter. Such;`

'aromatic hydrocarbons, as willl be understood,

may "comprise afraction produced bypyrogenetic conversion of paraflin' and naphthene hydrocarj y' v bons-at elevated temperatures.v

' elealteuti.v unsaturatedhydrocarbons passingal Similarly the present process may be utilized to eect a 'condensation reaction between unsaturated or oleflnic hydrocarbons and parafnic hydrocarbons. In these circumstances, straight run gasoline or similar hydrocarbon oil fractions may be utilized as4 the carryingvehicle for the bauxite.

Conditions may be so chosen that normally gaseous parafiins, such as propane, may be caused to undergo a condensation reaction with the gaseous olens associated with them.

Likewise, as will be appreciated, the process is available for the high temperature cracking of parailnic or saturated hydrocarbon gases. Such a process may be conducted in the type of apparatus shown, in which the parafnic gases are cracked at elevated temperatures of the order of 1000 F., in the reactor I2, in contact with the preferred type of catalyst and/or promoters described herein.

It will be understood that the broad concept of the invention involves the idea of accelerating or facilitating a polymerization and/or condensation reaction involving unsaturated hydrocarbons with or without other hydrocarbons, such as saturated aliphatic and aromatic hydrocarbons. Depending upon the type of charging stock utilized in the system and the type of iinal product desired, the polymerization and/or condensation reaction may be effected at ordinary pressure, but much more effectively at superatrnospheric pressures of the order of 1000 pounds per square. inch. The pressures however may be varied over any desirable wide range.

It will be understood that the type of processes herein dened present decided advantages. Due to the peculiar ecacy of the catalytic material or mixtures employed, the desired polymerization or condensation reactions may readily be effected. 'I'he catalytic materialsl employed, as will be appreciated, comprise cheap and readily available materials. While the use of nitrosyl chloride, as such, has been described, it is to beunderstood that in the operation of the process this material may be produced at the plantor may be produced in situ in any suitable phase of the process. such as bauxite, aluminum oxide, and powdered aluminum have been described, it is to be understood that any equivalent material having a benecial promoting function o'n the reaction may be employed.

While preferred modifications of the invention' have been described, it is to be understood that these are given merely to explain'the underlying principles of the invention and are not to be taken as the exclusive methods or means by which such principles` may be commercially effectuated.

I claim:

l. A method of producing low boiling liquid hydrocarbons which comprises contacting normally gaseous olenic hydrocarbons with nitrosyl chloride and bauxite, and condensing and collecting the condensable hydrocarbons formed.

Similarly, while preferred promoters,.

2. A method of producing low boiling liquid .hydrocarbons which -comprises contacting normally gaseous olenic hydrocarbons -with nitrosyl chloride and aluminum oxide, at elevated temperatures, and condensing and collecting the condensable hydrocarbons formed.

3. A method of producing-low boiling liquid hydrocarbons which comprises contacting gaseous oleiinic hydrocarbons with nitrosyl chloride at elevated temperatures in the presence of an oxide promoter chosen from the group consisting of aluminum oxide, zinc oxide, stannic oxide and .oxides of the alkaline earth metals.

4. A method of producing low boiling liquid hydrocarbons which comprises contacting normally gaseous oleflnic hydrocarbons with nitrosyl chloride and bauxite at temperatures of 'the order of from 100 F. to 400 F.

5. A method oi' polymerizing gaseous oleflnic hydrocarbons to produce low boiling liquid hydrocarbons therefrom which comprises heating the said hydrocarbons in their reaction zone in contact with nitrosyl chloride and at temperatures suiliciently high to effect` polymerization of the hydrocarbons, condensing, and collecting the liquid hydrocarbons so formed. L v

6. A method of producingl low boiling liquid hydrocarbons from normally gaseous oleiinic hydrocarbons which comprises contacting the olenic hydrocarbons at elevated temperatures with nitrosyl chloride and powdered aluminum in a heated reaction zone, passing the products of reaction to a distillation zone and there distilling the lighter fractions of the products of conversion and condensing and collecting such lighter fractions.

" 7. A method of producing improved motor fuels which comprises charging a stream of normally gaseous oleilnic hydrocarbons to a reaction zone; heating such hydrocarbons in the reaction zone to elevated temperatures in contact with a catalytic material comprising nitrosyl chloride, maintaining the reactive mass in the reaction zone for a period of time to insure polymerization of the hydrocarbons; withdrawing the products of `conversion from the reaction zone and fractionating such products to recover a light liquid hydrocarbon fraction therefrom.

8. A method of producing improved motor fuels which comprises charging normally gaseous oleiinic hydrocarbons to a reaction zone; heating the hydrocarbons in such zone to elevated temperatures in contact with a catalytic material comprising nitrosyl chloride, maintaining the mass in the reaction zone for a period of time suiiicient to insure the polymerization of the hydrocarbons; withdrawing the products of polyinerization and subjecting such products to fractionation to produce a gasoline-like fraction and a lighter gaseous fraction, and recycling such gaseous fraction to the reaction zone for retreatment.

1 MORRIS LEVINE. 

